Color photographic material and process



or in the color development process.

Uted States COLOR PHOTOGRAPHIC MATERIAL AND PROCESS Bela Gaspar, BeverlyHills, and Gustave B. Linden, North Hollywood, Cahfl; said Gasparassignor to Gasparcolor, In'c., Hollywood, Calif., a corporation ofDelaware No Drawing. Original application May 8, 1951, Ser. No. 225,267.Divided and this application Sept. 18, 1953, Ser. No. 381,413

1'4 Claims. (Cl. 96-53) Onthe other hand,

atent their resistance to diffusion keeps them from being washed out orfrom wandering from those discrete portions of the colloid into whichthey were incorporated.

Many methods are proposed by which soluble nondiffusing dye formingcompounds may be obtained. However, most of these methods lead tocompounds which are insufliciently soluble or which diffuse too much;the introduction of non-diffusing radicals into their moleculediminishes their solubility, or the introduction of solubilizingradicals into their molecule increases their tendency to diffuse.Furthermore, most of the known non-diffusing radicals ballast themolecule of the dye forming compound to a very high degree whereby,during the processing of the photographic material, dyes of lowtinctorial strength are produced. y

Many of the soluble, non-diffusing dye forming compounds hitherto knownhave still other disadvantages: e.g., they desensitize the lightsensitive emulsion, they crystallize, or they thicken the colloid. Someof them are made by complex and expensive synthesis or by methods oflimited scope.

It is therefore an object of the present invention to producephotographic dye images in light sensitive emulsions by means ofsoluble, non-diffusing dye-forming compounds which do not have the abovementioned disadvantages. A further object of the present invention is animproved preparation, isolation and purification method for resinsulfochlorides and the reactionproducts thereof. Further objects andadvantages will be seen from the detailed specification followinghereafter.

It has been found that dye-forming compounds RII' HN and HOR (of whichthe first ones are preferred) where R stands fora radical comprising afunctional group whereby the compound acts as a dye forming compound,where R stands for hydrogen, alkyl or aryl, and where R" stands for anaromatic radical having an available l l mg 2,943,934

coupling position, are rendered non-dilfusing by reactin with compoundswhere at least some of the Ys stand for the group I or -OR or -NHR" andwhere some of the Ys may stand for chlorine and after hydrolysis for an.O--

cation group.

The functional group in the radical R can be a phenolic, enolic,aromatic amino or any other group whereby the compound becomes reactivewith the oxydation products of developing compounds, with diazocompounds, with azo coupling compounds or with other dye formingreagents. Suitable radicals R are, e.g., thosederived from acetoaceticacid, pyrazolone, naphtholsulfonic acid, naphthylamine,diazoaminobenzene, phenylhydrazine, etc. However, we prefer thosecompounds which function as azo coupling components, and in second line,those which function as color development components. The preferredcomponents therefore, can be exemplified by:

The compounds ROI-l can be exemplified by 1,5-dihydroxynaphthalene andp-acetoacetamido phenol. Aromatic amines NH R" such as l-naphthylaminereacting with a polymeric sulfochloride form compounds having theformula These compounds where'the residue R" has an available couplingposition can couple in alkaline medium with diazo compounds or with theoxydation products of color developers to form dyes. r

The compound can be obtained by chlorosulfonation of compounds (--A'-)or by sulfonation of these compounds, fol- Patented July 5, 1960 lowedby conversion of the sulfonic acid into a sulfochloride group. In theseformulas A stands for an organic radical and It stands for an integergreater than 2. A will equal A and n will equal 11 in those cases whereone sulfochloride group is attached to each of the A' units. Another wayconsists in the polymerization of sulfonated monomeric compounds.

The preferred way of obtaining the compound in treating a compound (A')where A comprises an aromatic nucleus with chlorosulfonic acid.Compounds of the type (-A'-),,/ are known to be converted into sulfonicacids by treatment with chlorosulfonic acid; but we prefer to use-morechlorosulfonic acid than previous workers did, in order to obtainsulfochloride groups. The reaction is carried out in one operation inthe presence of a suitable solvent such as halogenated or unhalogenatedsaturated aliphatic hydrocarbons, i.e., carbontetrachloride,trichloroethane, ethylene chloride, heptane. We found that in performingthis operation the proportion of organic solvent to chlorosulfonatingagent is of considerable importance and should be chosen in such amanner that the reaction mixture remains essentially homogeneous. Wehave found that the above mentioned organic solvents dissolve most ofthe unsulfonated starting materials but tend to precipitate thesulfonation products before the desired number of sulfochloride groupshave entered the molecule. We, therefore, use a sufficient excess ofchlorosulfonic acid to keep the sulfonation product in solution at leastin the early stages of the reaction. After having obtained the desiredsulfochloride, the quantity of organic solvent is increased, whereby thesulfochloride is precipitated. In other words: A compound (A--)dissolved in a small amount of organic solvent, is chlorosulfonated withan excess of chlorosulfonic acid, and the sulfochloride formed isprecipitated with a large amount of organic solvent. While it wasalready known to react polystyrene with chlorosulfonic acid, no processfor the preparation and isolation of the sulfochloride per so wasdescribed. According to the German Patent No. 580,366, polystyrene wasreacted with less than the equivalent amount of chlorosulfonic acid,which procedure results in polystyrene sulfonic acid.

The compound (-A') can be any organic compound containing recurringunits A'-- which are capable of carrying sulfohalide groups. (--A) maybe a compound obtained by polymerization or mixed polymerization ofunsaturated compounds or by polycondensation of polyfunctional monomericcompounds or it may be a natural polymeric compound. E.g., (---A'---),,'may be polystyrene, natural rubber, an interpolymer of styrene andmaleic anhydride, polyvinylnaphthalene, polyvinylcarbazole or thecondensate of a dicanboxylic acid with a diamine.

Among suit-able compounds we mention the following:

A compound obtained by chlorosulfonation of polystyrene; a compoundobtained by sulfonation of styrenepolysulfone (Journ. Am. Chem. Sec.,59, 709 (1937)), followed by treatment with PO1 a compound obtained byPCl treatment of a rubber sulfonic acid (German Patent 582,565); acompound obtained by PCl treatment of an interpolymer ofethylenesulfonic acid with methyl methacrylate (U.S. Patent 2,348,705);the chloride of a sulfonic acid described in German Patent 503,- 923which was obtained by sulfonation of an anisol .formaldehydecondensation product; the compound obtained by simultaneouspolymerization and chlorosulfonation of benzylchloride essentially as inExample 8 of US. Patent 2,445,569, but replacing the sulfuric withchlorosulfonic acid; the chloride of a sulfonic acid obtained bycondensation of sulfosuccinic acid with ethylenediamine, and having theformula (U.S. Patent 2,252,401); a compound obtained bychlorosulfonation of dimethoxydinaphthylhydrorubber (Helv. Chim. Acta,10, 536 (1927)); a compound obtained by chlorosulfonation of thecondensation product formed from adipic acid and m-phenylenediamine, andhaving the formula a compound obtained by condensing 1:1 hydroquinonewith trimethylenebromide, by sulfonating the condensation product and bytreating the sodium salt of this sulfonic acid with phosphorouspentachloride, said compound having the formula S0201 S0201 (-O MHFOHPCMnQ In some of these compounds the SO Cl groups are attached to aliphaticcarbon atoms; in other compounds they are attached to aromatic carbonatoms.

From a compound, obtained by interpolymerization of ethyl vinylsulfonatewith styrene, a variety of derivatives can be obtained: The compound canbe saponified and treated with PCl whereby an aliphatic sulfochloride isobtained; or the saponified product is treated with excess ofchlorosulfonic acid whereby a mixed aliphatic aromatic sulfochloride isobtained; or the compound is treated with chlorosulfonic acid and, afterreaction with an amine, saponified whereby an aliphatic sulfonic acid ofan aromatic sulfonamide is obtained.

The molecular weight of the above mentioned sulfochlorides may varywithin wide limits; however we prefer the use of sulfochlorides derivedfrom polymeric hydrocarbons which hydrocarbons have molecular weights ofbetween 1000 and 10,000. If the degree of polymerization is too high, asulfochloride is obtained which, upon saponification, swells in aqueoussodium hydroxide without dissolving; the dye forming compound formedfrom such sulfochloride will be insufficiently soluble or thicken theemulsion. On the other hand, if the degree of polymerization is too low(e.g., in the sulfochlorides of dimerized olefines), the dye formingcompound will dilfuse appreciably. In indicating the preferred degree ofpolymerization, however, we want it to be understood that still otherfactors infiuence the properties of the compound. E.g., a color couplerderived from polystyrene 15,000 and comprising -SO Na groups (=62%) inthe molecule is more soluble than a similar product derived frompolystyrene 2000 and comprising only 4 SO Na groups (=2l%) in themolecule. Those compounds NH R and I-IOR which combine sclubilizingsalt-forming groups [such as'the above mentionedN-(arninobenzoyl)-Hacidl can be reacted with the sulfochlorides thenature of the functional residue.

in equivalent proportion. The compounds, thereby obtained, adhere to theformula S O aY where all the Ys stand for the group OR-- or --NHR".However, those compounds NHgR" and HOR which are void of solubilizingsalt forming groups, are reacted with an excass of sulfochloride, andthe sulfochloride groups in excess are saponified whereby compounds areobtained where some of the Ys stand for O- cation groups. The cation ispreferably hydrogen or an alkali metal depending on which product can beisolated conveniently.

The number of free O cation groups necessary for completesolubiliz-ation depends on the character of the radical A, on the degreeof polymerization (n) and on It must be determined empirically in eachcase which degree of polymerization and which number of free sulfonicacid groups is necessary to produce compounds having desirablequalities. However, we found in most cases that non-diffusing and wellsoluble dye-forming compounds of good tinctorial strength are obtainedby reacting one molecular part of a compound HOR or NI-I (void ofsolubilizing groups) with 1.5 to 5 equivalents of a compound j SOzCl Thedye-forming compounds of this invention do not difiuse on account of thehighly polymeric sulfonyl radical attached to the molecule. The fastnessto diffusion therefore is independent from the functional radicalattached to said sulfonyl radical. For example, all the derivatives ofpolystyrenesulfonic .acid are non-diffusing, and it does not matterwhether these derivatives were obtained by reactingpolystyrenesulfochloride with diffusing low molecular weight aminophenolor with a substantive amino-aryl-u'rea.

The fastness to diffusion, found in the dye-forming compounds of thisinvention, therefore is conserved in the derivatives obtained from thedye-forming compounds. For example, if a non-difiusing azocouplingcomponent of this invention is coupled with a diazo compound, anazo dye is formed'which still contains the polymeric sulfo residue andtherefore does not difiuse.

Whereas, in the prior art, each soluble non-diffusing dye formingcompound must be individually tailored, the synthesis of these compoundsis greatly simplified by the .present invention. All that is needed isone polymeric sulfochloride which may be used universally for all dyeforming compounds containing amino or hydroxyl groups by which they canbe attached tothe sulfochloride. The fact that sulfochloride groups areused for introducing the solubilizing groups (S0 H) into the molecule,and that sulfochloride groups are used for rendering the dye fromforming monomeric component fast to diffusion, allows this simpleprocedure which does away with introducing non-diffusing radicals andsolubilizing radicals into a dye forming molecule.

It shall be clearly understood that the general formulais not meant torepresent a chemical individual. Polymers (A'.),,' from which thecompounds of our invention are obtained, might contain terminal groupswhich are different from groups in the middle of the chain.Irregularities such as branchings might occur within the otherwiselinear molecule. The symbol n might stand for a statistical valueinstead of one integer. Similarly, the number of sulfonic acid orsulfonamide groups within the molecule might vary within certain limits;e.g., the sulfonation of a compound (A),,' with chlorosulfonic acid maylead to a product in which only 50% of the aromatic nuclei carrysulfochloride groups or in which some of the aromatic nuclei carry morethan one sulfochloride group. The formulae disclosed herein thereforecannot be regarded as complete structural representations, but merelyserve to illustrate those features of the molecules which are consideredessential for understanding their behavior.

The dye-forming compounds, obtained according to our novel method, aredissolved in water and added to a photographic colloid such as gelatin,vinyl alcohol, cellulose glycolic acid, polyacrylamide. Thosedye-forming compounds which were isolated asdiflicultly soluble freeacids are dissolved in aqueous alkali to form the easily soluble salts,and these salt solutions are then stirred the compounds, may be coatedas a layer on a support or as a discrete'particle within a layer. Thelightsensitive agent such as silver halide, might be within that portionof the colloid which comprises the dyeforming compounds of our inventionor it might be in an adjacent portion. The photographic material maycomprise only one dye-forming compound, or may comprise a plurality ofdiscrete portions and a plurality of dye forming compounds. A

The dye-forming compounds of this invention are colored or colorless.Among the colored ones we mention those azo dyes which are capable ofcoupling with diazo compounds or of reacting with the oxidation prodnetsof color developing agents. However, we prefer those dye-formingcompounds which are colorless. These colorless dye-forming compounds areincorporated in colorless photographic materials or in materialscomprising light screening elements such as yellow filter layers. Thedye-forming molecule might also be a part of the carrier or bindingagent for the silver halide or other light sensitive materials.

The light sensitive photographic material comprising a dye-formingcompound of this invention is subjected to the usual photographicprocesses including those whereby the dye-forming compound is convertedinto aj dye and those whereby the latent silver image is converted intoa proportional or reversed dye image. Among these processes we mentionthe color development and the dyebleach process. Other. processes arewell within the scope of the present inventions. However, the preferredprocess consists in producing an azo dye by coupling the dye-formingcompound with a diazo compound at a point after the exposure to lightand by destroying the diazo. compound or the azo dye at those pointswhere metallic silver has been developed.

The following examples will serve to illustrate the manner of obtainingour new compounds and of using them in photographic materials.

Example 1 Twenty-five parts by weight of Dow Resin PS1 (which is apolystyrene of molecular weight 6000, manufactured and sold by the DowChemical Company) were dissolved in 80 parts by volume of ethylenechloride. This solution was added to chlorosulfonic acid parts byvolume) over a period of 2 hours while the temperature was kept below 0C., and the mixture, forming a nearly homogeneous solution, was stirredfor an additional 3 hours at this temperature. The next day a fewundissolved particles were removed by filtration and discarded. The:chlorosulfonated resin was precipitated by addition of 700 parts byvolume of ethylenechloride, the liquid was decanted, the residue waswashed with three portions ofethylene' chloride (each portion amountingto 250 parts by volume) and purified by dissolving in acetone andprecipitating from this solution by the addition of benzene. Theprecipitate was a nearly colorless solid which dissolved in acetone ordimethylformamide or, after heating, in aqueous sodium hydroxidesolution.

By determination 'of the sulfochloride groups it was found that thecompound has an equivalent weight of 215, indicating a 95%chlorosulfonation.

A similar compound was obtained by treating Dow Resin PS-2 (polystyrene,molecular weight 9000) in the above manner.

Example 2 The sulfochloride of the foregoing example (2.5 equivalentparts) was dissolved in acetone.N-(m-aminobenzenesulfo)-1,5-aminonaphthol (1.0 equivalent part) andpyridine (2.5 equivalent parts) were dissolved in acetone. This solutionwas slowly added with stirring and cooling to the sulfochloridesolution. The reaction was completed by heating to reflux. A resinousmass separated which was dissolved, by heating, in 1 n NaOH, andprecipitated from the alkaline solution with 1 n HCl.

The compound is believed to be a linear molecule, having about 22 units:

and about 33 units:

-CH-OH2- soar and about 3 units:

CH-CH2 It is soluble in aqueous sodium bicarbonate solution. The neutralsolution can be added to a photographic silver halide emulsion. Anemulsion, containing 7% gelatin and 0.8% of this dye-forming compoundcan be coated by normal procedures. The presence of this dyeformingcompound does not influence the light sensitivity of silver bromideemulsions sensitized to blue, green or red light. If coated in amultilayer material, no wandering of the compound from layer to layertakes place, as can be shown by development with p-diethylaminoanilineor by coupling with a diazo component.

The compound obtained from the sulfochloride of Example 1 and1,5-aminonaphthol has similar properties. These compounds, when coupledwith diazotized 4-nitro- 1-naphthylamine-6-sulfonic acid, yield azo dyeswhich are cyan above pH 7.

Example 3 The sulfochloride of Example 1 (2 equivalent parts) is reactedwith N,N-dimethyl-m-phenylenediamine (1 equivalent part) in a similarmanner as described in the previous example. The compound therebyobtained is believed to have essentially. the following constitutionSOaH SOFNH The compound is colorless, easily soluble, does not diffusewithin a photographic colloid, doesnot desensitize a silver halideemulsion and reacts easily with diazo compounds to form dyes of hightinctorial strength.

The compound obtained from the sulfochloride of Example 1 andN,N-dirnethyl-N-p-aminobenzoyl-rn-phenylenediamine has similarproperties. Diazotized 2- nitraniline-4-sulfonic acid couples with thesecompounds to produce azo dyes which are magenta at pH' 8.

Example 4 A compound of the following probable constitution2-)4((l)H-CHz)1]12 S0311 SOr-NH-O is obtained by condensing 5:1 thesulfochloride of Example 1 withN-(m-aminophenyl)-1,2,3,4-tetrahydro-2,4- dioxoquinoline. The compoundhas all the qualities mentioned for the compound of the previousexample. The azo dye obtained from this compound and diazotized 2-nitraniline-4-sulfonic acid is yellow.

Example 5 Four layers are coated on a transparent support in thefollowing order:

(1) A red-sensitized gelatin silver bromide emulsion containing a cyancoupler obtained by condensing 2 equivalents of polystyrenesulfochlorideand 1 equivalent of 1,5-aminonaphthol and by hydrolizingthe' unreactedsulfochloride groups.

(2) A green-sensitized gelatin silver bromide emulsion containing amagenta coupler obtained by condensing 2 equivalentsof-polystyrenesulfochloride and 1 equivalent of m-diethylaminoanilineand by hydrolizing the unreacted sulfochloride groups.

(3) A filter layer comprising gelatin and colloidal silver.

(4) An only blue sensitive gelatin silver bromide emulsion containing ayellow coupler obtained by condensing 3.4 equivalents ofpolystyrene-sulfochloride with 1 equivalent of6-amino-2,4-dihydroxyquinoline and by hydrolizing the unreactedsulfochloride groups.

The material is exposed in a camera, developed in an alkaline metolhydroquinone developer, and fixed in an acid hypo bath. Thereafter itisbathed for 10 minutes in 1% Duponol ME (a wetting agent manufactured andsold by Du Pont Company) and then bathed for 12 minutes at 5 C. in abath comprising 60 grams glacial acetic acid 2.5 grams sodium acetateanhydrous 4 grams 4-nitro-1-diazobenzene-2-sulfonic acid Water to make 1liter.

In this bath, the diazo compound reacts with'the three coupler compoundsto form azo dyes which, at pH 8, arecyan, magenta and yellowrespectively. These dyes absorption maxima of the cyan and magenta azodyes are shifted to longer wavelengths. colors is obtained.

The silver bromide emulsions of the first, second and fourth layers withand without the coupler compounds were compared sensitometrically. Thepresence of the coupler compounds had no influence on the sensitivity ofthe emulsions.

An image in natural Example 6 Equimolecular parts of diethylmaleate andstyrene were refluxed in the presence of catalytic amounts ofbenzoylperoxide. After the initial reaction subsided the temperature waskept at 130 C. for 6 hours.

The mass was dissolved in benzene and precipitated with an isopropanolmethanol mixture. This operation was repeated several times. A whitepowder was obtained.

This compound was dissolved in ethylene dichloride and chlorosulfonatedby the procedure of Example 1. A tan powder was obtained which wassoluble in acetone. After the saponification with aqueous sodiumhydroxide, it was soluble in aqueous sodium acetate or bicarbonatesolutions.

The compound servedin the acylation of dye-forming compounds such asl-(p-aminobenzoylamino)--naphthol; N,N-dimethyl-m-phenylenediamine;N,N-dimethyl-N'-paminobenzdyl-m-phenylenediamine; m-diethylaminophenyl,8-(p-aminophenoxy)ethyl ether; 1,2,3,4-tetrahydro-2,4-dioxo-6-aminoquinoline. All these compounds were well soluble, did notdilfuse and reacted with diazo compounds, to form azo dyes of hightinctorial strength.

We have found that the sulfochloride of this example can be reacted withcomponents void of solubilizing groups in equivalent proportions, andthat the dye-forming compoundsthereby formed are soluble as carboxylicacid salts in aqueous media, after hydrolizing the carboxylic estergroups of the reaction products; e.g., by digesting with aqueous alkali.However, if reacted with less than the equivalent quantity of acomponent, some of the sulfochloride groups will be converted to formsulfonic acid groups which increase the solubility of the product.

For example, we prepared a compound from this acid chloride and1,5-aminonaphthol in a proportion of 2:1 which we believe to have thefollowing constitution The compound is soluble in aqueous sodiumbicarbonate solutions. It can replace the compound of Example 2 inphotographic applications such as those of Example 5. The letter n inthe above formula stands for a whole number greater than 1.

Example 7 A material to be used in the color development process can, bemade by the following procedure: Four layers are coated on one side of atransparent support, viz:

(1) A silverbromide emulsion, sensitized for red light and containingthe product obtained by condensing 2 equivalents ofpolystyrenesulrfochloride with 1 equivalent of 18- (p-aminophenoxy)ethyl-m-hydroxyphenyl ether and by hydrolizing the unreactedsulfochloride groups.

(2) A silverbromide emulsion, sensitized for green light and containingthe product obtained by condensing 2.0 equivalents ofpolystyrenesulfdchloride with 1 equivalent ofl-(p-aminophenyl)-3-methyl-5-pyrazolone, and by hydrolizing theunreacted sulfochloride groups.

(3) A yellow filter layer comprising colloidal silver.

(4) A silverbromide emulsion, void of optical sensitizer and containingthe product obtained by condensing 3.0 equivalents ofpolystyrenesulfochloride with 1 equivalent of m-amino(acetoacetanilide)and by hydrolizing the unreacted sulfochloride groups.

The material is exposed to light in a camera, developed in an amidoldeveloper, exposed to diffuse light and then developed in a developercontaining per one liter solution:

- Grams p-Amino diethylaniline hydrochloride 2.0 Sodium sulfiteanhydrous 5.0 Sodium carbonate anhydrous 20.0

After the silver is removed in a potassium ferricyanide sodium chloridebath followed by a hypo bath, an image in natural colors is obtained.

Example 8 Two equivalents of the sulfochloride of Example 1 are reactedwith one equivalent of p-nitrophenol. The unreacted sulfochloride groupsare hydrolized, and-the reaction product is reduced with iron filings indiluted acetic acid suspension. The compound obtained is believed toadhere essentially to the following fo'rmula Example 9 The polymericamine of the foregoing example can serve as a skeleton from which otherdye components may be prepared. By reacting the polymeric amine with anexcess of salicylchloride in aqueous sodium acetate solution, a solublenon-diifusing product is obtained which forms yellow dyes with mostdiazo compounds and cyan dyeswith color developers containingp-aminodiethyl-- aniline. 1

Example 10 A compound of the following probable structure (-()H-CH2')about on SOz-NH OH I KOzS- -sotK is prepared by'dissolving free H-acid'(1 equivalent) and cetyldimethylarnine (4 equivalents) inmethyl-i-butylketone, by distilling olf part of the ketone to assureabsolute exclusion of humidity, and by adding to the cold solution asolution of polystyrenesulfochloride (1 equivalent) in acetone. Thehomogeneous solution is refluxed for 15 minutes and cooled. The reactionproduct is precipitated as potassium salt by addition of a rnethanolidKOH solution. The solid is washed with acetone and purified by saltingout with potassium carbonate from aqueous solution. It is a watersoluble tan powder.

A photographic layer, comprising this compound, is exposed to light,developed, fixed, coupled with a diazo compound, treated'in a dyebleachbath and freed from silver to produce a dye image which is inversed withrespect to the silver image. The addition of the compound to the silverbromide emulsion does not depress the light sensitivity. A gelatinemulsion layer comprising the compound, co'ated between other gelatinemulsion layers, and processed as above, contains the dye image only inthe middle layer; no diffusion is detectable. The colo'r of the dyeimage depends on the diazo compound used in the process. E.g., bycoupling with 4-nitro-2-sulfodiazobenzene, a magenta image is produced,whereas, by coupling with 4-diazo-4-ethoxydiphenylamine, a blue image isproduced.

The free H-acid, used in this example is obtained from the acid bariumsalt of H-acid and sulfuric acid.

Example 11 Q (LN When incorporated into a photographic emulsion, exposedand developed with a developer comprising p-amine-diethylaniline, thisproduct couples to form a cyan dye at those places where metallic silveris developed. A more bluish shade is obtained if the salicyl-(m-aminoanilide) of this example is replaced with1-(paminophenyl)--pyrazolone-3-carboxylic acid.

Example 12 Two equivalents of the sulfochloride of Example 1 are reactedwith one equivalent of l-naphthylamine in an acetone pyridine mixtureand the unreacted sulfochloride groups are hydrolized. The reactionproduct serves as a component in a photographic layer. When coupled with4-nitro-2-sulfodiazobenzene it forms a dye which is purple in alkalinemedium and weakly yellow in acid medium. When it is coupled with theoxydation product of p-aminodiethylaniline it forms a blue dye.

Example 13 The red and green sensitive emulsions of Example 5 are dyedyellow with N-p-tolyl-auramine. These emulsions and the blue sensitiveemulsion of Example 5 are hardened, spray-dried,- mixedand coated. Thematerial is exposed and processed in the same manner as the material ofExample 5. An image in natural colorsis obtained.

Example 14 A red sensitive gelatin silver chloride emulsion containingthe cyan coupler of preceding Example 7, a green sensitive silverchloride emulsion containing the magenta coupler of Example 7 and a bluesensitized silver chloride emulsion containing the yellow coupler ofExample 7 are hardened with chrome alum, spraydried, mixed in a 1%gelatin solution and coated on a support. The material is exposed tolight through a #4 Wratten filter and treated in the same way as thematerial of Example 7.

The silver chloride emulsions of this example can be replaced withsilver chlorobromide emulsions containing up to 30% bromide.

We claim:

1. A photographic material comprising an emulsion layer containing alight-sensitive silver halide and a watersoluble non-diffusingdye-forming compound containing -SO cation solubilizing groups and saiddye-forming compound comprising a high molecular weight polymeric linearchained radical of the group consisting of polymeric hydrocarbonradicals, polymeric oxahydrocarbon radicals, and polymeric carboxylicacid amide radicals having recurring amide groups in the main linearpolymeric chain, said polymeric radical carrying a plurality of SO Ygroups outside the main linear polymeric chain, wherein Y is a radicalselected from the group consisting of azo dye coupling components and aradical capable of coupling with the oxidation products of a primaryaromatic amino color developer to form a dye, said radical Y beingattached to the S0 radical by the valence bond of an atom selected fromthe group consisting of nitrogen and oxygen, said SO Y groups beinglinked to the main'linear chain of said polymeric radical only throughcarbonatoms selected from the group consisting of carbon atoms of phenylnuclei and carbon atoms of the main linear chain.

2. A photographic material comprising an emulsion layer containing alight-sensitive silver halide and a watersoluble non-diffusingdye-forming compound containing SO cation solubilizing groups and saiddye-forming compound comprising a high molecular weight polymeric linearchained radical of the group consisting of polymeric hydrocarbonradicals, polymeric oxahydrocarbon radicals, and polymeric carboxylicacid amide radicals having recurring amide groups in the main linearpolymeric chain, said polymeric radical carrying a plurality of SO Ygroups outside the main linear polymeric chain, wherein Y is a radicalselected from the group consisting of azo dye coupling components and aradical capable of coupling with the oxidation products of a primaryaromatic amino color developer to form a dye, said radical Y beingattached to the S0 radical by the valence bond of a nitrogen atom, saidSO Y groups being linked to the main linear chain of said polymericradical only through carbon atoms selected from the group consisting ofcarbon atoms of phenyl nuclei and carbon atoms of the main linear chain.

3. A photographic material comprising an emulsion layer containing alight-sensitive silver halide and a water soluble non-diffusingdye-forming compound containing SO cation solubilizing groups and saiddye-forming compound comprising a high molecular weight styrene polymercarrying a plurality of -SO Y groups in the phenyl nuclei of saidstyrene polymer, wherein Y is a radical selected from the groupconsisting of azo dye coupling components and a radical capable of.coupling with the oxidation products of a primary aromatic amino colordeveloper to form a dye, said radical Y being attached to the S0 radicalby the valence bond of an atom selected from the group consisting ofnitrogen and oxygen.

4. 1m a-process =forpr'oducing a colored image in a photographicmaterial, the steps which comprise exposing a light-sensitive silverhalide emulsion layer containing a water-soluble dye-forming compoundcontaining SO cation solubilizing groups and said dye-formingcompoundcomprising a high molecular weight polymeric linear chainedradical of the group consisting of polymeric hydrocarbon radicals,polymeric oxahydrocarbon radicals, and polymeric carboxylic acid amideradicals havmg recurring amide groups in the main linear polymericchain, said polymeric radical carrying a plurality of -SO Y groupsoutside the main linear polymeric chain, wherein Y is a radical selectedfrom the group consisting of azo dye coupling components and a radicalcapable of coupling with the oxidation products of a primary aromaticamino color developer to form a dye, said radical Y being attached tothe S radical by the' valence bond of an atom selected from the groupconsisting of nitrogen and oxygen, said SO Y groups being linked to themain linear chain of said polymeric radical only through carbon. atomsselected from the group consisting'of. carbonatoms of phenyl nuclei andcarbon atoms of the main linear chain, and forming a dye in said layerfor said colored image comprising said polymeric radical by a couplingreaction. a

5. In a process for producing a colored image in a photographicmaterial, the steps which comprise exposing a light-sensitive silverhalide emulsion layer containing a water-soluble non-difiusing azocoupling component containing SO cation solubilizing groups and said azocoupling component comprising a high molecular weight polymeric linearchained radical of the group consisting of polymeric hydrocarbonradicals, polymeric oxahydrocarbon radicals, and polymeric carboxylicacid amide radicals having recurring amide groups in the main linearpolymeric chain, said polymeric radical carrying a plurality of -SO Ygroups outside the main linear polymeric chain, wherein Y is an azo dyecoupling component radical which is reactive with adiazo compound toform an azo dye comprising said polymeric radical, said radical Y beingattached to the S0 radical by the valence bond of an atom selected fromthe group consisting of oxygen and nitrogen atoms, said SO Y groupsbeing linked to the mainlinear chain of said polymeric radical onlythrough carbon atoms selected from the group consisting of carbon atomsof phenyl nuclei and carbon atoms of the main linear chain, couplingsaid azo coupling component with a diazo compound to form an azo dye insaid layer, developing and fixing said layer to forma metallic silverimage in said layer and treating said layer to destroy said dye locallyin the presence of said metallic silver image.

6. A process for producing a colored image in a photographic layercontaining a metallic silver image and a water-soluble non-diffusing azocoupling component containing SO cation solubilizing groups and said azocoupling component comprising a high molecular weight polymeric linearchained radical of the group consisting of polymeric hydrocarbonradicals, polymeric oxahydrocarbon radicals, and polymeric carboxylicacid amide radicals having recurring amide groups in the main linearpolymeric chain, said polymeric radical carrying a plurality of SO Ygroups outside the main linear polymeric chain, wherein Y is an azo dyecoupling component radical which is reactive with a diazo compound forforming an azo dye comprising said polymeric radical, said radical Ybeing attached to the S0 radical by the valence bond of an atom selectedfrom the group consisting of oxygen and nitrogen atoms, said SO Y groupsbeing linked to the main linear chain of said polymeric radical onlythrough carbon atoms selected from the group consisting of carbon atomsof phenyl nuclei and carbon atoms of the main linear chain, couplingsaid azo coupling component with a diazo compound to form an azo dye insaid layer and-treating said layer to destroy said dye locally in thepresence of said metallic silver image.

v V 14 v 7. A process for producing a colored image in a photographiclayer containing a light-sensitive silver halide and as a color former awater-soluble non-diffusing compound containing SO cation solubilizinggroups and said compound comprising a high molecular weight polymericlinear chained radical of the group consisting of polymeric hydrocarbonradicals, polymeric oxahydrocarbon radicals, and polymeric carboxylicacid amide radicals having recurring amide groups in the main linearpolymeric chain, said polymeric radical carrying a plurality of SO Ygroups outside the main linear polymeric chain, wherein Y is a radicalcapable of coupling with the oxidation products of a primary aromaticamino color developer to form a dye, said radical Y being attached tothe S0 radical by the valence bond of an atom selected from the groupconsisting of oxygen and nitrogen atoms, said SO Y groups being linkedto the main linear chain of said polymeric radical only through carbonatoms selected from the group consisting of carbon atoms of phenylnuclei and carbon atoms of the main linear chain, which comprisesexposing said layer and developing said layer with a primary aromaticamino color developer.

8. A photographic material comprising an emulsion layer containing alight-sensitive silver halide and a watersoluble non-diffusingdye-forming compound containing SO cation solubilizing groups and saiddye-forming compound comprising a high molecular weight polymeric linearchained hydrocarbon radical carrying a plurality of -SO Y groups outsidethe main linear polymeric chain, wherein Y is a radical selected fromthe group consisting of azo dye coupling components and a radicalcapable of coupling with the oxidation products of a primary aromaticamino color developer to form a dye, said radical Y being attached tothe S0 radical by the valence bond of an atom selected from the groupconsisting of nitrogen and oxygen, said SO Y groups being linked to themain linear chain of said polymeric radical only through carbon atomsselected from the group consistingof carbon atoms of phenyl nuclei andcarbon atoms of the main linear chain.-

9. In a process for producing a colored image in a photographicmaterial, the steps which comprise exposing a light-sensitive silverhalide emulsion layer containing a water-soluble non-dilfusingdye-forming compound containing SO cation solubilizing groups and saiddye-forming compound comprising a high molecular weight polymeric linearchained hydrocarbon radical carrying a plurality or" -SO Y groupsoutside the main linear polymeric chain, wherein Y is a radical selectedfrom the group consisting of azo dye coupling components and a radicalcapable of coupling with the oxidation products of a primary aromaticamino color developer to form a dye, said radical Y being attached tothe S0 radical by the valence bond of an atom selected from the groupconsisting of nitrogen and oxygen, said SO Y groups being linked to themain linear chain of said polymeric radical only through carbon atomsselected from the group consisting of carbon atoms of phenyl nuclei andcarbon atoms of the main linear chain, and forming a dye in said layerfor said colored image containing said polymeric hydrocarbon radical, bya coupling reaction.

10. In a process for producing a colored image in a photographicmaterial, the steps which comprise exposing a light-sensitive silverhalide emulsion layer containing a water-solube non-diffusingdye-forming compound containing SO cation solubilizing groups and saiddyeforming compound comprising a high molecular weight styrene polymercarrying a plurality of -SO Y groups in the phenyl nuclei of saidstyrene polymer, wherein Y is a radical selected from the groupconsisting of azo dye coupling components and a radical capable ofcoupling with the oxidation products of a primary aromatic amino colordeveloper to form a dye, said radical Y being at tached to the S0radical by the valence bond of an atom selected from the groupconsisting of nitrogen and oxygen, and forming a dye in said layer forsaid colored image containing said styrene polymer, by a couplingreaction.

11. A silver halide emulsion containing as a non-diffusing color formera polymeric coupler prepared by reacting a polyvinyl sulfonyl. chloridewith an amino-substituted color former capable of reacting with theoxidation product of a primary aromatic amino developing agent.

12. A silver halide emulsion containing as a non-diffusing color formera polymeric coupler having recurring units of the structure:

(1'2) n-k-SOzNHR' where R is a group containing an aryl radical, R is acolor former capable of reacting with the oxidation prod net of aprimary aromatic amino developing agent, including an aryl group and nis an interger from 1 to 2.

13. A silver halide emulsion containing as a nondiffusing color former apolymeric coupler having recurring units of the structure:

where R is a color former capable of reacting with the oxidation productof a primary aromatic amino develop ing agent, including an aryl group.

14. The process of producing color developed dye images in aphotographic silver halide emulsion which comprises exposing theemulsion of claim 12 and developing it with a primary aromatic aminodeveloping agent.

References Cited in the file of this patent UNITED STATES PATENTS2,289,804 Peterson July 4, 1942 2,306,410 Schinzel Dec. 29, 19422,356,759 Gaspar Aug. 29, 1944 2,422,680 Jennings June 24, 19472,470,769 Gaspar May 24, 1949 2,688,542 Dreyfuss Sept. 7, 1954 FOREIGNPATENTS 551,120 Great Britain Feb. 8, 1943 651,958 Great Britain Apr.11, 1951

1. A PHOTOGRAPHIC MATERIAL COMPRISING AN EMULSION LAYER CONTAINING ALIGHT-SENSITIVE SILVER HALIDE AND A WATERSOLUBLE NON--DIFFUSINGDYE-FORMING COMPOUND CONTAINING -SO3 CATION SOLUBILIZING GROUPS AND SAIDDYE-FORMING COMPOUND COMPRISING A HIGH MOLECULAR WEIGHT POLYMERIC LINEARCHAINED RADICAL OF THE GROUP CONSISTING OF POLYMERIC HYDROCARBONRADICALS, POLYMERIC OXAHYDROCARBON RADICALS, AND POLYMERIC CARBOSYLICACID AMIDE RADICALS HAVING RECURRING AMIDE GROUPS IN THE MAIN LINEARPOLYMERIC CHAIN, SAID POLYMERIC RADICAL CARRYING A PLURALITY OF -SO2YGROUPS OUTSIDE THE MAIN LINEAR POLYMERIC CHAIN, WHEREIN Y IS A RADICALSELECTED FROM THE GROUP CONSISTING OF AZO DYE COUPLING COMPONENTS AND ARADICAL CAPABLE OF COUPLING WITH THE OXIDATION PROUDCTS OF A PRIMARYAROMATIC AMINO COLOR DEVELOPER TO FORM A DYE, SAID RADICAL Y BEINGATTACHED TO THE SO2 RADICAL BY THE VALENCE BOND OF AN ATOM SELECTED FROMTHE GROUP CONSISTING OF NITROGEN AND OXYGEN, SAID -SO2Y GROUPS BEINGLINKED TO THE MAIN LINEAR CHAIN OF SAID POLYMERIC RADICAL ONLY THROUGHCARBON ATOMS SELECTED FROM THE GROUP CONSISTING OF CARBON ATOMS OFPHENYL NUCLEI AND CARBON ATOMS OF THE MAIN LINEAR CHAIN.